Polyester polyol-containing polyurethane systems having improved hydrolytic stability

ABSTRACT

An isocyanate reactive composition for making a polyurethane foam includes a tertiary amine urethane catalyst comprising a di(C1-C4)alkyl fatty alkyl amine and a polyester polyol. The use of one or more of fatty alkyl tertiary amine serves to reduce hydrolysis of the polyester polyol in the isocyanate reactive composition.

FIELD OF THE INVENTION

The invention relates to polyurethane products and methods for producingthem. More particularly, it relates to catalysts for improving thehydrolytic stability of certain isocyanate reactive compositions formaking polyurethane foams.

BACKGROUND OF THE INVENTION

In molded polyester polyurethane systems or systems using flameretardant, the hydrolytic stability of the system is very important. Forexample, in spray foams, polyester polyols and flame retardants are usedbecause they can improve the fire performance of the final product but,upon storing a polyester polyol and flame retardant in the presence ofwater and tertiary amine, decomposition of the polyester to acid andpolyol occurs causing the amine to form a salt. The tertiary aminecatalyst becomes acid blocked reducing the reactivity of the system,often rendering it unsuitable for use. This problem is particularlyserious in spray foams where systems with very high reactivity arerequired because the reaction mixture is expected to react very fast asit is sprayed over a surface. If the reactivity is decreased, thespraying mass of material cannot adhere to the surface causing it todrip or sag, and solidify at a different location than the sprayingpoint. In addition, due to the high reactivity required in spray foams,high use levels of tertiary amines are required which combined withwater present in the systems causes the polyester polyol to hydrolyzemuch faster than in other polyester systems.

Isocyanate reactive compositions containing polyester polyols for makingpolyurethane (PU) foam are typically mixed with water, flame retardants,amine catalysts, metal catalysts, surfactants and other additives formaking polyurethane foams. Polyester polyol and flame retardants arecharacterized by their poor hydrolytic stability in such reactivecompositions. Their hydrolytic instability is particularly enhanced inthe presence of alkali such as tertiary amines which are normallypresent in the PU systems as catalysts.

The presence of tertiary amine catalysts causes the polyester polyol andflame retardant to hydrolyze to the corresponding glycols and acidcausing the acid to neutralize the tertiary amine reducing the overallreactivity of the system which has serious implications on the kineticsand properties of the final product.

BRIEF SUMMARY OF THE INVENTION

In one aspect, the invention provides an isocyanate reactive compositioncomprising a polyester polyol, water, a catalyst composition comprisingat least one particular tertiary amine urethane catalyst and optionallya fire retardant or a Mannich polyol, or both. The compositionoptionally may also include one or more blowing agents, crosslinkers,additional urethane catalysts and surfactants. The particular tertiaryamine is a di(C1-C4)alkyl (fatty alkyl) amine of formula (1)R1R2NR3  (1)where R1 and R2 are independently C1-C4 alkyl groups and R3 is a fattyalkyl of C8-C36.

As another embodiment, the invention provides compositions for makingpolyurethane foam comprising the contact product of an organicpolyisocyanate and the isocyanate reactive composition comprising apolyester polyol, water, a catalyst composition comprising one or moretertiary amine urethane catalysts of formula (I) and optionally a fireretardant or a Mannich polyol, or both. In a further aspect thepolyurethane foam compositions comprise rigid PU foam compositions.Rigid spray foams contain urethane, urea and isocyanurate linkages. Inthe present invention, “polyurethane” includes urethane, urea and/orisocyanurate linkages.

In another aspect, the invention provides a method for making apolyurethane foam. The method combines a polyisocyanate and theisocyanate reactive composition comprising a polyester polyol, water, acatalyst composition comprising at least one tertiary amine urethanecatalyst of formula (I) and optionally a fire retardant or a Mannichpolyol, or both.

The use of the catalyst composition can reduce polyester polyoldecomposition (hydrolysis) allowing for more shelf stability. Inaddition, the catalyst composition can be used to make polyurethanespray foams with low odor and good foam kinetics and physicalproperties.

The ability to improve hydrolysis stability in conventional and highresilience polyurethane slabstock foams, and flexible moldedpolyurethane foam, as well as in spray rigid foam, is important.

DETAILED DESCRIPTION OF THE INVENTION

One aspect of the invention relates to tertiary amine catalystcompositions and isocyanate reactive compositions for makingpolyurethane foams. The catalyst compositions include at least onecompound which is a dialkyl(fatty alkyl) tertiary amine. The inclusionof one or more of these tertiary amines serves to reduce hydrolysis ofpolyester polyols in the isocyanate reactive compositions. Thedialkyl(fatty alkyl) tertiary amine compounds may be used in conjunctionwith conventional urethane catalysts under otherwise conventionalconditions to make polyurethane foams. The foams are made by combiningat least one polyisocyanate compound, at least one polyester polyolcompound, and a urethane catalyst composition comprising at least onedialkyl(fatty alkyl) tertiary amine. A blowing agent is usuallyincluded, but need not be.

Fatty Alkyl Tertiary Amine

As used herein, the term “fatty alkyl tertiary amine” means a compoundor mixture of compounds according to the formulaR1R2NR3where R1 and R2 are independently C1-C4 alkyl groups and R3 is a fattyalkyl of C8-C36, especially C10-C22. In another aspect the fatty alkylis C12-C18. The C1-C4 alkyl groups include methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. Fatty alky groupsinclude butyric, caproic, caprylic, capric, lauric, myristic, palmitic,stearic, linoleic, myristoleic, palmitoleic, oleic, linoleic, linolenicand ricinoleic.

Suitable for use in the invention are dimethyldecyl amine,dimethyldodecyl amine, dimethyltetradecyl amine, dimethylhexadecylamine, dimethyloctadecyl amine, dimethylcoco amine, dimethyloleyl amine,dimethylricinoleyl amine, diethyldecyl amine, diethyldodecyl amine,diethyltetradecyl amine, diethylhexadecyl amine, diethyloctadecyl amine,diethylcoco amine, diethyloleyl amine, diethylricinoleyl amine,dipropyldecyl amine, dipropyldodecyl amine, dipropyltetradecyl amine,dipropylhexadecyl amine, dipropyloctadecyl amine, dipropylcoco amine,dipropyloleyl amine, dipropylricinoleyl amine, dibutyldecyl amine,dibutyldodecyl amine, dibutyltetradecyl amine, dibutylhexadecyl amine,dibutyloctadecyl amine, dibutylcoco amine, dibutyloleyl amine anddibutylricinoleyl amine.

The fatty alkyl tertiary amines are commercially available or can beprepared by hydrogenation followed by reductive alkylation of thecorresponding fatty nitrites. Fatty nitrites are obtained from thecorresponding acids via amidation of their ammonium salts followed bydehydration of amides. The manufacture of the fatty tertiary amines iswell known in the art as evidenced by both patent literature and theopen literature.

Other Urethane Catalysts

The catalyst compositions in the isocyanate reactive compositions of thepresent invention in addition to the fatty alkyl tertiary amine also maycomprise any urethane catalysts well known in the art, especially otherknown tertiary amine urethane catalysts.

In one aspect of the invention pertaining to making polyurethane foams,especially spray rigid foams, any gelling and/or blowing catalyst knownin the art may be used in combination with the fatty tertiary amine. Agelling catalyst is any tertiary amine catalyst known in the urethaneart with an initial selectivity of less than 0.7. A blowing catalyst isany tertiary amine catalyst known in the urethane art with an initialselectivity of greater than 0.7. Catalyst selectivity is defined as theratio of the rate of blowing (urea formation) to the rate of gelling(urethane formation) [J. Cellular Plastics, Vol. 28, 1992, pp. 360-398].

Thus the catalyst composition comprising the fatty alkyl tertiary aminecan also contain one or more tertiary amine gelling and/or blowingcatalysts. Suitable gelling catalysts may include, for example,triethylenediamine (TEDA), quinuclidine, pentamethyidipropylenetriamine,dimethylcyclohexyl amine, tris(dimethylaminopropyl)-amine, substitutedimidazoles such as 1,2-dimethylimidazole and1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU),N,N-bis(3-dimethylaminopropyl) N-isopropanol-amine;N,N-dimethylaminoethyl-N′-methyl ethanolamine;N,N,N′-trimethylaminopropyl ethanolamine; N,N-dimethylethanolamine;N,N-dimethyl-N′,N′-2-hydroxy(propyl)-1,3-propylenediamine;dimethylaminopropylamine; N,N,N″,N″-tetramethyldipropylene-triamine;N,N-bis(3-dimethylaminopropyl)-1,3-propanediamine;N-dimethylaminopropyl-N-methylethanolamine; substituted quinuclidines(U.S. Pat. No. 5,143,944 and U.S. Pat. No. 5,233,039); substitutedpyrrolizidines (U.S. Pat. No. 5,512,603); substituted pyrrolidines (EP499 873); (N,N-dimethylaminoethoxy)ethanol;methylhydroxyethylpiperazine; bis(N,N-dimethyl-3-aminopropyl)amine; ureacompounds of tertiary amines such as N,N-dimethylamino-propyl urea andN,N′-bis(3-dimethylamino-propyl)urea; bis(dimethylamino)-2-propanol;N-(3-aminopropyl)imidazole; N-(2-hydroxy-propyl)-imidazole; andN-(2-hydroxyethyl) imidazole.

Suitable blowing catalysts include but are not restricted tobis(dimethylaminoethyl) ether, pentamethyldiethylenetriamine and relatedcompositions (U.S. Pat. No. 5,039,713, U.S. Pat. No. 5,559,161), higherpermethylated polyamines such as permethylated triethylenetetramine(U.S. Pat. No. 4,143,003), and branched polyamines (U.S. Pat. No.3,836,488), 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol andrelated structures (U.S. Pat. No. 4,338,408), alkoxylated polyamines(U.S. Pat. No. 5,508,314), imidazole-boron compositions (U.S. Pat. No.5,539,007), and aminopropyl-bis(aminoethyl)ether compositions (U.S. Pat.No. 5,874,483 and U.S. Pat. No. 5,824,711); dimethylaminoethoxyethanol;N,N,N′-trimethyl-N′-3-amino-propyl-bis(aminoethyl) ether; andN,N,N′-trimethyl-N′-aminopropyl-bis(aminoethyl) ether.

Trimerization catalysts may be use in combination with the fatty alkyltertiary amine, especially for spray rigid foam systems, and include anysuch catalysts known in the art. Specific examples includeN-hydroxyalkyl quaternary ammonium carbonylate or carboxylate salts,such as are disclosed in U.S. Pat. No. 4,582,861. Also useful are alkalimetal carboxylate salts. One exemplary carboxylate salt is potassium2-ethylhexanoate, also known as potassium octoate.

For systems other than spray foam systems, some or all of the gelling,blowing, and trimerization catalyst may be “blocked” with (i.e. a saltformed with) a carboxylic acid salt, a phenol, or a substituted phenol,assuming that the catalyst contains amine functionality with which toform a salt to provide for a delayed onset of catalyst activity.

The catalyst compositions may also include other components, for examplemetal catalysts such as organotin compounds like dibutyltin dilaurate,for example when the desired polyurethane foam is a flexible slab stock.

The amount of fatty alkyl tertiary amine in the isocyanate reactivecomposition should typically be 0.05 to 20 parts per hundred partspolyol on a weight basis (pphp). More typically, the amount will be 0.1to 10 pphp, and most typically 0.4 to 5 pphp. The spray foam systemsrequire a higher amount of the fatty alkyl tertiary amine than otherfoam systems, thus the high upper limit for the fatty alkyl tertiaryamine.

In terms of the catalyst composition the fatty alkyl tertiary amine maycomprise 100 to 5 wt %, preferably 50 to 10 wt % of such composition. Anespecially desirable catalyst composition comprises 10 to 40 wt %pentamethyldiethylenetriamine, 20 to 80 wt % tris(dimethylaminopropyl)amine and 10 to 50 wt % fatty alkyl tertiary amine. In another aspectthe catalyst composition comprises 15 to 30 wt %pentamethyldiethylenetriamine, 35 to 65 wt % tris(dimethylaminopropyl)amine and 20 to 40 wt % fatty alkyl tertiary amine.

Polyisocyanate

Polyurethanes prepared using the catalyst compositions of this inventionmay be made from any of a wide variety of polyisocyanates known in theart. Examples of suitable polyisocyanates include hexamethylenediisocyanate (HDI), phenylene diisocyanate (PDI), toluene diisocyanate(TDI), and 4,4′-diphenylmethane diisocyanate (MDI). Especially suitableare the 2,4-TDI and 2,6-TDI individually or together as theircommercially available mixtures. Other suitable mixtures ofdiisocyanates are those known commercially as “crude MDI”, also known asPAPI, which contain about 60% of 4,4′-diphenylmethane diisocyanate alongwith other isomeric and analogous higher polyisocyanates. One example ismarketed by Dow Chemical Company under the name PAPI, and contains about60% of 4,4′-diphenylmethane diisocyanate along with other isomeric andanalogous higher polyisocyanates.

Also suitable are “prepolymers” of these isocyanate compounds comprisinga partially pre-reacted mixture of a polyisocyanate and a polyether orpolyester polyol to convert one or more hydroxyls on the polyesterpolyol to substituted carbamate groups. Suitable prepolymers derivedfrom polyether and polyester polyols are well known in the art.

Polyols

The present invention pertains to the use of a fatty alkyl tertiaryamine-containing catalyst composition for making polyester polyol-basedpolyurethane foams. Any polyester polyol known in the art can be used,including those produced when a dicarboxylic acid or anhydride isreacted with an excess of a diol. Non-limiting examples include adipicacid or phthalic acid or phthalic anhydride reacting with ethyleneglycol or butanediol. However, most common polyester polyols are madefrom phthalic, isophthalic and terephthalic acids. Esterification ofthese acids with polyol initiators such as ethylene glycol, diethyleneglycol, propylene glycol, dipropylene glycol, butanediol, polyethyleneglycols of various molecular weights, glycerin, pentanetriol, and thelike can yields polyester polyols with different physical properties,molecular weights and molecular architectures but all characterized bytheir poor hydrolytic stability. Also, polyester polyols useful in thepresent invention can be produced by reacting a lactone with an excessof a diol, for example, caprolactone reacted with propylene glycol.

The polyol component of the isocyanate reactive composition may alsocomprise other polyols known in the art in addition to the polyesterpolyols. Such other suitable polyols known in the art for makingpolyurethane formulations catalyzed by the catalyst compositions of theinvention include the polyalkylene ether polyols. The polyalkylene etherpolyols include poly(alkylene oxide) polymers such as poly(ethyleneoxide) and poly(propylene oxide) polymers and copolymers having terminalhydroxyl groups derived from polyhydric compounds including diols andtriols, such as for example ethylene glycol, propylene glycol,1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol,diethylene glycol, dipropylene glycol, pentaerythritol, glycerol,diglycerol, trimethylol propane, cyclohexanediol and like low molecularweight polyols.

Amine polyether polyols can also be used in the present invention. Thesecan be prepared when an amine such as, for example, ethylenediamine,diethylenetriamine, tolylenediamine, diphenylmethanediamine, ortriethanolamine is reacted with ethylene oxide or propylene oxide.

Mannich polyols are also used in spray foam formulations to increase thereactivity of the system. Mannich polyols are typically prepared bycondensation of phenol with formaldehyde in the presence of hydroxylcontaining amines such as diethanolamine, ethanolamine and the like.

In another aspect of the present invention, a single high molecularweight polyether polyol, or a mixture of high molecular weight polyetherpolyols, such as mixtures of different multifunctional materials and/ordifferent molecular weight or different chemical composition materialscan be used.

In addition to the base polyols described above, or instead of them,materials commonly referred to as “copolymer polyols” may be included ina polyol component for use according to the invention. Copolymer polyolsmay be used in polyurethane foams to increase the resistance of the foamto deformation, for example to improve the load-bearing properties ofthe foam. Depending upon the load-bearing requirements for thepolyurethane foam, copolymer polyols may comprise from 0 to about 80percent by weight of the total polyol content. Examples of copolymerpolyols include, but are not limited to, graft polyols and polyureamodified polyols, both of which are known in the art and arecommercially available.

Blowing Agents

Polyurethane foam production may be aided by the inclusion of a blowingagent to produce voids in the polyurethane matrix during polymerization.Any blowing agent known in the art may be used. Suitable blowing agentsinclude compounds with low boiling points which are vaporized during theexothermic polymerization reaction. Such blowing agents are generallyinert and therefore do not decompose or react during the polymerizationreaction. Examples of inert blowing agents include, but are not limitedto, carbon dioxide, chlorofluorocarbons, hydrogenated fluorocarbons,hydrogenated chlorofluorocarbons, acetone, and low-boiling hydrocarbonssuch as cyclopentane, isopentane, n-pentane, and their mixtures. Othersuitable blowing agents include compounds, for example water, that reactwith isocyanate compounds to produce a gas.

Fire Retardants

The most common flame retardants used in PU foam formulations aretris(2-chloropropyl)phosphate (TCPP), tris(2-chloroethyl)phosphate(TCEP), dimethylmethylphosphonate (DMMP), and diethylene glycol (DEG)and propylene glycol (PG) esters of tetrabromophthalic anhydride(ME-TBPA). These flame retardants can exhibit various stages ofstability in the isocyanate reactive compositions. Needless to say,other known fire retardants can also be used.

Other Optional Components

A variety of other ingredients may be included in the formulations formaking foams according to the invention. Examples of optional componentsinclude, but are not limited to, cell stabilizers such as silicones,crosslinking agents, chain extenders, pigments, fillers and combinationsof any of these. Suitable chain extenders for use include ethyleneglycol, 1,4-butanediol, and combinations of these.

Contact Product

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time. Combining additional materials orcomponents can be done by any method known to one of skill in the art.Further, the term “contact product” includes mixtures, blends,solutions, slurries, reaction products, and the like, or combinationsthereof. Although “contact product” can include reaction products of oneor more components with each other, it is not required for therespective components to react with one another.

In the following examples and tables use levels of the components otherthan the polyols are in pphp (parts by weight per hundred parts polyols)unless indicated otherwise. General exemplary polyurethane formulationscontaining fatty alkyl tertiary amine catalyst compositions according tothe invention may include formulations such as set forth in Tables 1-3.

A general spray rigid foam formulation according to the invention inwhich the urethane catalyst composition also includes a trimerizationcatalyst would comprise the following components in parts by weight(pbw):

TABLE 1 Spray Rigid Foam Formulation Component Parts by Wt (pphp)Polyester Polyol 10-100 Mannich Polyol 0-90 Polyether Polyol 0-90Blowing Agent 5-40 Silicon Surfactant 0.2-5   Water 0-10 Amine Catalyst0-20 Metal Catalyst 0-20 Trimerization Catalyst 0.1-10   Fatty AlkylTertiary Amine Catalyst 0.05-20   Isocyanate Index (NCO Index) 80-500

Spray rigid foams typically are made using polyester polyols of about220 to 5000 weight average molecular weight (Mw) and hydroxyl number(OH#) of about 20 to 450.

TABLE 2 Flexible Foam Formulation Component Parts by Wt (pphp) Polyetherand Polyester Polyols 20-100 Co-Polymer Polyol (e.g.,styrene-acrylonitrile 0-80 polyol) Silicone Surfactant 0.2-2.5  BlowingAgent  2-4.5 Crosslinker (e.g., diethanolamine) 0.5-3   Catalyst 0.1-5  Isocyanate (NCO Index) 70-115 Index

TABLE 3 Rigid Foam Formulation Component Parts by Wt (pphp) Polyol 100Silicone Surfactant 0.2-4 Blowing Agent   2-35 Water   0-5 Catalyst0.1-5 Isocyanate (NCO Index)   70-300 IndexPreparation of Foams

Foams may be made according to the methods known in the art usingtypical polyurethane formulations to which have been added a urethanecatalyst composition comprising one or more fatty alkyl tertiary amines.

The amount of polyisocyanate used in polyurethane formulations accordingto the invention is not limited, but it will typically be within thoseranges known to those of skill in the art. Exemplary ranges are given inthe Tables, indicated by reference to “NCO Index” (isocyanate index). Asis known in the art, the NCO index is defined as the number ofequivalents of isocyanate, divided by the total number of equivalents ofactive hydrogen, multiplied by 100. The NCO index is represented by thefollowing formula.NCO index=[NCO/(OH+NH)]×100

In some embodiments of the invention, the fatty alkyl tertiary aminecatalyst composition may be combined into a package with one or morepolyester polyols, and optionally with one or more blowing agents and/orother additives commonly used in polyurethane formation. Examples ofthese other optional components have been listed previously, and they donot affect the basic nature of the invention. Such mixtures maysubsequently be combined with an organic isocyanate to form apolyurethane foam, again optionally in the presence of other additivesknown in the art.

In addition to making rigid spray foams, the invention may also be usedto prepare flexible slabstock and molded foams and semi-flexible foams,such as are commonly utilized for many applications in the automotiveindustry (e.g., instrument panels and interior trims).

Example Hydrolysis Stability Study for Different Amine Catalysts

The following isocyanate reactive, or B-side premix, composition wasused to compare the impact that various urethane catalysts had on thehydrolysis stability of the polyester polyols. The premix compositionswere stored at 120° C. and samples were taken every seven days todetermine the acid content. The acid content was determined bysolubilizing samples in a 1:1 mixture of toluene and ethanol. Acidnumber values were determined in duplicate by titration usingpotentiometric titrations. A Metrohm 835 Titrando and a MetrohmSolvitrode pH electrode were used for the acid number potentiometrictitrations. The titrant was 0.1N methanolic potassium hydroxide using a5 ml burette.

Premix Composition Component pphp* Polyester Polyol (OH# = 304) 50Mannich Polyol (OH# = 465) 50 Flame Retardant (TCPP) 21.5 Surfactant(Dabco DC193) 1.39 Catalyst Varied Water 3.06 *Parts per Hundred Polyol(wt)

The following components were used

-   -   TCPP—tris(2-chloropropyl)phosphate    -   DMEA—dimethylaminoethanol    -   PC-5—pentamethyldiethylenetriamine    -   PC-9—tris(dimethylaminopropyl) amine    -   B-16—dimethyloleyl amine    -   PC-30—blend of 20 wt % PC-5, 55 wt % PC-9, 25 wt % B16

TABLE 4 DMEA DMEA PC-5 PC-9 B-16 PC-30 Days 2.78* 1.39* 1.39* 1.39*1.39* 1.39* 0 0.655 0.638 0.624 0.608 0.608 0.604 7 2.990 2.325 1.5171.640 1.272 1.537 14 5.592 4.037 2.404 2.615 1.990 2.509 *pphp

Table 4 shows the values of the acid numbers of the compositionsprepared with different catalysts over a period of two weeks. The higherthe acid number the more hydrolysis has occurred in the compositionbecause acidity is formed by polyester polyol hydrolysis. After 24 daysDMEA, an industry standard for making spray foam, showed the largestacid number and the B-16 fatty alkyl tertiary amine showed the lowestindicating the greatest hydrolysis stability of the amine compositionstested. The PC-30 composition comprising B-16 dimethyloleyl amine showedreduced hydrolysis compared to DMEA and also afforded good foam rate ofrise kinetics.

The invention claimed is:
 1. An isocyanate reactive compositioncomprising at least one polyester polyol, at least one Mannich polyol,water and a urethane catalyst composition comprising dimethyloleylamine.
 2. The composition of claim 1 further comprising a fireretardant.
 3. The composition of claim 1 in which the urethane catalystcomposition further comprises at least one other tertiary amine urethanecatalyst.
 4. The composition of claim 1 in which the urethane catalystcomposition comprises 10 to 40 wt % pentamethyldiethylenetriamine, 20 to80 wt % tris(dimethylaminopropyl)amine and 10 to 50 wt % dimethyloleylamine.
 5. A polyurethane foam composition comprising the contact productof a polyisocyanate and an isocyanate reactive composition comprising apolyester polyol, water and a urethane catalyst composition comprisingdimethyloleyl amine.
 6. The polyurethane foam composition of claim 5further comprising a fire retardant.
 7. The polyurethane foamcomposition of claim 6 further comprising a Mannich polyol.
 8. Thepolyurethane foam composition of claim 7 in which the urethane catalystcomposition comprises at least one other tertiary amine urethanecatalyst.
 9. The polyurethane foam composition of claim 5 in which theurethane catalyst composition comprises 10 to 40 wt %pentamethyldiethylenetriamine, 20 to 80 wt %tris(dimethylaminopropyl)amine and 10 to 50 wt % dimethyloleyl amine.10. The polyurethane foam composition of claim 7 comprising one or moreblowing agents.
 11. A method of making a polyurethane foam, the methodcomprising combining at least one polyisocyanate and an isocyanatereactive composition comprising at least one polyester polyol, at leastone Mannich polyol, at least one flame retardant, at least onesurfactant, water and a urethane catalyst composition comprisingdimethyloleyl amine.
 12. The method of claim 11 wherein the polyesterpolyol comprises 10-100 pphp of the reactive composition.
 13. The methodof claim 11 wherein the surfactant comprises a silicon surfactant andthe silicon surfactant comprises 0.2-5 pphp of the reactive composition.14. The method of claim 11 wherein the catalyst composition furthercomprises at least one member selected from the group consisting ofamine catalysts, metal catalysts, and trimerization catalysts.
 15. Themethod of claim 11 wherein the foam has an NCO index of 80 to
 500. 16.The composition of claim 1 further comprising at least one memberselected from the group consisting of triethylenediamine, quinuclidine,pentamethyldipropylenetriamine, dimethylcyclohexyl amine,tris(dimethylaminopropyl)-amine, 1,2-dimethylimidazole,1,8-diazabicyclo-[5.4.0]undec-7-ene, N,N-bis(3-dimethylaminopropyl)N-isopropanol-amine; N,N-dimethylaminoethyl-N′-methyl ethanolamine;N,N,N′-trimethylaminopropyl ethanolamine; N,N-dimethylethanolamine;N,N-dimethyl-N′,N′-2-hydroxy(propyl)-1,3-propylenediamine;dimethylaminopropylamine; N,N,N″,N″-tetramethyldipropylene-triamine;N,N-bis(3-dimethylaminopropyl)-1,3-propanediamine;N-dimethylaminopropyl-N-methylethanolamine;(N,N-dimethylaminoethoxy)ethanol; methylhydroxyethylpiperazine;bis(N,N-dimethyl-3-aminopropyl)amine; N,N-dimethylamino-propyl urea,N,N′-bis(3-dimethylamino-propyl)urea; bis(dimethylamino)-2-propanol;N-(3-aminopropyl)imidazole; N-(2-hydroxy-propyl)-imidazole; andN-(2-hydroxyethyl)imidazole.
 17. The composition of claim 1 furthercomprising at least one member selected from the group consisting ofbis(dimethylaminoethyl)ether, pentamethyldiethylenetriamine,permethylated triethylenetetramine,2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol, alkoxylatedpolyamines, imidazole-boron compositions,aminopropyl-bis(aminoethyl)ether compositions;dimethylaminoethoxyethanol;N,N,N′-trimethyl-N′-3-amino-propyl-bis(aminoethyl)ether; andN,N,N′-trimethyl-N′-aminopropyl-bis(aminoethyl)ether.
 18. Thecomposition of claim 1 further comprising at least one member selectedfrom the group consisting of N-hydroxyalkyl quaternary ammoniumcarbonylate and potassium 2-ethylhexanoate.
 19. The composition of claim1 further comprising at least one amine salt formed with a carboxylicacid salt, a phenol, or a substituted phenol.
 20. The composition ofclaim 1 further comprising at least one member selected from the groupconsisting of cell stabilizers, crosslinking agents, chain extenders,pigments, and fillers.
 21. The composition of claim 20 wherein the chainextenders comprise at least one of ethylene glycol and 1,4-butanediol.22. The composition of claim 5 wherein the polyisocyanate comprises atleast one member selected from the group consisting of hexamethylenediisocyanate, phenylene diisocyanate, toluene diisocyanate, and4,4′-diphenylmethane diisocyanate.